Polyazo-dyestuffs



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. POLYAZO-DYESTUFFS Richard Huss, Arthur Siebert, and Josef Weissert, Frankfurt anr Main, Germany, assignors to Farbwerke Hoechst Aktiengesellschaft vormals Meister Lucius &

Bruning, Frankfurt am Main, Hochst, Germany, a company'of Germany No Drawing. Application June 29,1953 ySerial No. 3fi 4,910

Claims priority, application Germany July 2, 1952 5 Claims. (Cl. 260-144) The present inventionrelates to new polyazo-dyestufis;

more particularly it relates to the polyazo-dyestulfs, corresponding to the following general formula B t-N=N wherein R and R represent aromatic radicals, X stands for the diphenyl bond the sulfonic acid group, and wherein the-phenyl radicals a may contain substituents.

We have found that new valuable polyazo-dyestuffs corresponding to the general constitution N H2 acid NH: X 9 are obtained by coupling 1 molecular proportion of a tetrazotized diamine of the general formula NH: I NH:

Q in which X has the meaning indicated above and the two phenyl radicals may contain substituents, in an acid medium with 1 molecular proportion of a 1-amino-8-hy- *ldroxynaphthalene-monoor disulfouic acid and combining the diazoazo-compound thus obtained with 1 molecular proportion of any diazoor diazoazo-compound and '1 molecular proportion of 3.3"-dihydroxydiphenylamine. The resulting polyazo-dyestufis may be used as such for dyeing leather. Since the 3.3'-dihydroxydiphenylamine is capable of coupling-twice, it is possible to obtain valuable higher polyazo-dyestufi's by combining the said polyazo-dyestuifs with a further diazoor diazoazo-compound which may contain one or more sulfonic acid groups. s The invention also includes an alternative process for making polyazo-dyestulfs of the above constitution, wherein 1 molecular proportion of the tetrazotized diamino-compound is coupled in an acid medium with 1 molecular proportion of a 1-amino-8-hydroxynaphthalenemonoor disulfonic acid, the diazoazo-compound so obtained is combined with 1 molecular proportion of a di- ElZOfiZCd' amine and'the' resulting diazopolyazo-compound l-amino-s-hydroxy- "amine naphthalene-monoor disulf nic acid 3.3'-dihydroxydi- (amine phenylamine' 2,885,390 Pate t d-Ma 5, .2

2 is coupled in an alkaline medium with l molecular pro: portion cf the azo-dyestulf from 3.3'-dihydroxy-diphenylamine and a sulfonated diazoor diazoazo-compound,

The invention also includes a further process for making the aforesaid polyazo-dyestufis, wherein 1 molecular proportion of the tetrazotized diamino compound coupled in an acid medium with 1 molecular proportion of a 1-amino-8-hydroxynaphthalene-monoor disulfonic acid, the diazoazo-compound soobtained is combinedin an alkaline medium with 1 molecular proportion of the azo-dyestutf from 3.3-dihydroxydiphenylamine and a sulfonated diazoor diazoazo-compound, and the resulting polyazo-dyestuif is coupled with 1 molecular proportion of a diazotized amine.

The invention also includes another process for making the aforesaid polyazo-dyestufis, wherein 1 molecular proportion of the tetrazotized diamino-compound is coupled in an acid medium with 1 molecular proportion of a 1-amino-8-hydroxynaphthalene-monoor disulfonic acid, the diazoazo-com pound so obtained is combined with 1 molecular proportion 'of 3.3'-dihydroxy-di heny1- amine, .andthe resulting ,disazo-dyestuff is coupled with 2 molecular proportions of the same or different"dia2o'- or dlazoazo-compound.

The invention also includes another process for making the aforesaid polyazo-dyestulfs, wherein 1 molecular proportion of the tetrazotized diamino-compound is coupled with 1 molecular proportion of a l-amino-8-hydroxynaphthalene-mono or disulfonic acid, the diazoazo-compound so obtained is combined with 1 molecular proportion of a diazotized amine, and the resulting diazopolyazo-compound and 1 molecular proportion of a diazoor diazoazo-compom-l are coupled simultaneously with 1 molecular proportion of 3.3-dihydroxy-diphenylamine.

The new dyestuffs are readily soluble in water and are resistant to inorganic and organic acids as well as to alkalies and formaldehyde. They have agreat-aflinity, for leather fibers, and dye t e various kinds of-leather, by drum dyeing, brush dyeing or spray dyeing, deep full tints which vary from violet, dark green over dark blue to black. y

In German Patent 566,471 is described a dyestutf of the following constitution acid aniline r l-amino-S-hy- 4.4-dir 3-hydroxydroxynaphthaaminodi- 2-met yl: 1ene-3.6-disulphenyl diphenyltonic acid amine acid sulfaniiic 1-amino-8-hy- 4.4-dil-amino-S. acid droxy-naphthaaminodihydroxylane-3.6-disulphenyl benzene ionic acid The new dyestufis obtainable by using 3.3'-dihydroxydiphenylamine are superior to the known dyestufis men- I tioned above generally with respect to their resistance to acids. They yield fuller surface dyeings and have much better penetrating and through-dyeing properties than the dyestuff described in British Patent 618,007.

The following examples serve to illustrate the invention but they are not intended to limit it thereto; the parts being by weight unless otherwise stated, and the relationship of parts by weight to parts by volume being the same as that of the kilogram to the liter:

Example 1 A tetrazo-solution prepared in the usual manner from 18.4 parts of 4.4-diaminodiphenyl is combined in an acid medium within 16 hours with 34.1 parts of l-amino-S- hydroxy-naphthalene-3.6-disulfonic acid (monosodium salt), the excess of the acid being removed by the addition of 3.5 parts of calcium carbonate. To the diazoazocompound so obtained a diazo-suspension prepared from 17.3 parts of l-aminobenzene-4-sulfonic acid is added in one portion and 36 parts of anhydrous sodium carbonate are then introduced. After 30 minutes, a weakly alkaline solution of 20.1 parts of 3.3'-dihydroxy-diphenylamine is poured in and the coupling is conducted at a pH-value of by adding 50 parts by volume of a 2 N- solution of sodium hydroxide. After stirring for 4 hours, the mixture is rendered acid with 100 parts by volume of 2 N acetic acid, salted out with sodium chloride, filtered off with suction and dried. The trisazo-dyestuff so obtained corresponds to the following formula:

OH NH:

It is readily soluble in water, resistant to sulfuric acid and dyes chrome-tanned leather deep reddish-black tints having a good covering power. The dyeings on bark-tanned leather and on velvet leather are especially valuable. The brush dyeings are distinguished by a very good covering power.

Example 2 A tetrazo-solution prepared in the usual manner from 18.4 parts of 4.4'-diaminodiphenyl is combined in an acid medium within 16 hours with 34.1 parts of l-amino- 8-hydroxy-naphthalene-3.6-disulfonic acid (monosodium salt), the excess of the acid being neutralized with 3.5 parts of calcium carbonate. To the diazoazo-compound so obtained a diazo-suspension prepared from 17.3 parts of l-aminobenzene-4-sulfonic acid is added in one portion and 36 parts of anhydrous sodium carbonate are then introduced. After 30 minutes a weakly alkaline solution of 20.1 parts of 3.3'-dihydroxydiphenylamine is added and the coupling is conducted at a pH-value of 10 in the presence of 50 parts by volume of a 2 N-solution of sodium hydroxide. The trisazo-dyestuff so obtained is stirred overnight. An aqueous diazo-suspension from 17.3 parts of 1-aminobenzene-4-sulfonic acid is then slowly added, while cooling, and the pH-value of the coupling medium is maintained at 10 by the addition of a 2 N- solution of sodium hydroxide. After stirring for 5 hours, the tetrakisazo-dyestuff is rendered acid with acetic acid, the mixture is heated to 90 C., rendered acid to Congo paper by adding 5 N-hydrochloric acid, precipitated with as small a quantity of sodium chloride as possible, filtered off with suction and dried. The grey-black powder so obtained is readily soluble in water, resistant to sulfuric acid and dyes chrome-tanned leather, by velvet and brush dyeing, deep black tints having a good covering power and very good fastness properties, especially a very good fastness to light.

Example 3 18.4 parts of 4.4-diaminodiphenyl are tetrazotized in the usual manner and the tetrazo solution is combined in an acid medium with 34.1 parts of l-amino-S-hydroxynaphthalene-3.6-disulfonic acid (monosodium salt), the excess of the acid being neutralized with 3.5 parts of calcium carbonate. When the coupling is complete, a diazosuspension prepared from 17.3 parts of l-aminobenzene- 4-sulfonic acid is added in one portion and 150 parts by volume of a 2 N-solution of sodium hydroxide are then introduced to obtain a pH-value of 10. After stirring for 30 minutes, a solution of 10 parts of 3.3'-dihydroxy-diphenylamine in 100 parts by volume of water and 10 parts by volume of a 10 N-solution of sodium hydroxide is then added, the pH-value of the coupling medium being maintained. The mixture is stirred overnight, rendered acid to Congo paper and filtered ofi with suction. The hexakisazo-dyestuff obtained in the form of a black powder dyes the various kinds of leather deep black tints with a distinctly blue hue which are distinguished by a good fastness to acids, alkalies and formaldehyde and a full covering power.

Example 4 184 parts of 4.4-diamino-diphenyl are tetrazotized in OH on SOIH the usual manner and the tetrazo-solution is coupled at a pH-value of 2 with a solution, having an acid reaction to litmus, of 319 parts of l-amino-8-hydroxynaphthalene- 3.6-disulfonic acid, the excess of the acid being neutralized with 35 parts of calcium carbonate. To the diazoazocompound so obtained a diazo-suspension prepared from 173 parts of l-aminobenzene-4-sulfonic acid is added at 5 C., and 2000 parts by volume of a 2 N-solution of sodium hydroxide are then introduced so that the coupling is completed at a pH-value of 10. The resulting diazodisazo-compound is combined, While maintaining the pH-value of 10, with the monoazo-dyestufi obtained by coupling in an alkaline medium 201 parts of 3.3-dihydroxydiphenylamine with the diazo-suspension prepared from 173 parts of 1-aminobenzene-4-sulfonic acid. When the coupling is complete, the tetrakisazo-dyestuff is acidified with 250 parts by volume of 5 N-hydrochloric acid, the mixture is heated to C., precipitated with sodium chloride, filtered 05 with suction and dried. The resulting dyestuif corresponds with respect to its dyeing and fastness properties with the dyestuff described in Ex ample 2.

Example 5 The diazoazo-compound obtainable as described in Example 4 from tetrazotized 4.4-diamino-diphenyl and 1- amino-8-hydroxy-naphthalene-3.6-disulfonic acid is combined at a pH-value of 10 with the monoazo-dyestuff prepared from the diazo-suspension of 173 parts of l-aminobenzene-4-sulfonic acid and 201 parts of 3.3'-dihydroxydiphenylamine. The trisazo-dyestufi so obtained is coupled, while maintaining the pH-value of 10, with a diazo- 5 suspension prepared from 173 parts of l-alminobenzene- '5 4-sulfonicacid -and, the product, is isolated. as. described in the foregoing examples. The tetrakisazo-dyestufi dyes the various kinds of leather covered reddish-black tints of good fastness properties.

- Example 6 To the diazoazo-compound from tetrazotized 4,4'-diaminodiphenyl and l amino-8-hydroxynaphthalene-3.6- disulfonic acid obtainable as described in Examples 1 and 2 a solution of 20.1 parts of 3,3-dihydroxy-diphenyl- 10 amine in parts by volume of a 10 N-solution of sodium hydroxide and 200 parts by volume of water is added and a suflicient quantity of a 10 N-solution of sodium hydroxide is then introduced so that the coupling occurs ata pH-value of 10. The disazo-dyestufi so obtained '15 is combined, while cooling, the diazo-suspension prepared from 34.6 parts of 1-aminobenzene-4-sulfonic acid and 200 parts by, volume of a 2 N-solution of sodium hydroxide are added simultaneously so that the coupling I medium is maintained at a pH-value of 10. The dye- 20 stuif-is stirred overnight, then rendered acid, heated to 90 C., precipitated with a small quantity of sodium manner. The grey-black peweer'ee obtained is readily soluble inwater and dyes allkinds of leather. byvarious methods of dyeing deep full black tints. having a good covering power, fastness to light and. resistance to inorganic and organic acids as well 'as' to formaldehyde and alkalies.

Example 8 0.1 molecular proportion of the t'ris2 1zo-dyes tulf ob. tainable as described in Example 1 which corresponds to the following constitution l-aminobenzene--sulfonic acid 7 acid l-ainino-8-hydroxynaphthalene-3.6-dlsulfonlc acid 4- '4.4-diaminodipheny1 r 3.3-dihydroxy-diphenylamine is combined in an alkaline medium with 0.1 molecular proportion of the diazodisazo-compound of the following formula chloride, filtered off with suction and dried. The week powder so obtained is readily soluble in water and dyes the various kinds of leather, by drum dyeing, brush dyeing or'spray dyeing, deep black tints of good covering power, very good fastnes's to light and very good general 40 fastness properties.

Example 7 A tetrazo-solution prepared in the usual manner from 21 parts of 4.4'-diaminostilbene is combined in an acid medium within 16 hours with, 34.1 parts of 1-amino-8- hydroxynaphthalene-3.6 disulfonic acid (monosodium introduced. After 30 minutes, an alkaline solution of 20.1

parts of 3.3'-dihydroxy-diphenylamine and a sufiicient quantity of a 2 N-solution of sodium hydroxide are introduced so that the coupling occurs in a strongly alkaline'medium. The trisazo-dyestutf is stirred overnight. While cooling, a diazo-suspension prepared from 17.3 parts of l-arninobenzenel-sulfonic acid is slowly added and simultaneously such a quantity of a 2 N-solution of sodium hydroxide that the alkaline reaction of the coupling medium is maintained. After stirring for 5 hours, the tetrakisazo-dyestufi' isI-isolated .in. the usual The' dyestuif -solution neutralized 'with acetic" acid. is heated to C., rendered acid. to, Congo; paper :and precipitated with a small quantity of sodium chloride. The dyestutf is obtained in the form of a grey-black powder which is readily soluble in water and dyes the various kinds of leather by drum dyeing, brush. dyeing and spray dyeing, bluish black tints of remarkably good fastness properties.

Example 9 0.1 molecular proportion of the pound of the following formula- H0 8 SOaH 60 is combined in an alkalinermedium with 0.1 molecular proportion of the trisazo-dyestuif obtainable by coupling in an acid medium the diazosuspension prepared from 17.3 parts of 1-aminobenzene-4-sulfonic acid with 34.1 parts of 1-amino-8-hydroxynaphthalene 3.6 disulfonic acid (monosodium salt), subsequently coupling the resulting monoazo-compound in a weakly alkaline medium while cooling, withthe tetrazo-solution prepared from 18.4 parts of 4.4'-diaminodiphenyl .and finally coupling with an alkaline solution of 20.1 parts of 3.3-"dihydroxydiphenylamine. The unsymmetrical hexakisazo-dyestuff is isolated as described in Example 8. The grey-black powder so obtained dyes the various kinds of leather greenish blue black tints of remarkably good resistance to inorganic and organic acids, formaldehyde and alkalies and a very good fastness to light. a

. Example 10 The alkaline solution of the diazo-disazo-compound which is obtained as described in Example 4 and has the following constitution alkaline 1-aminoben1cne-4-suiionic acid m ac i-smino-iS-hydroxynaphthaiene-3.6-disuiionic acid 4.4-diaminodiphenyl is stirred for /2 hour and then adjusted to a pH-value of 4 by adding the appropriate quantity of a 5 N-solution of hydrochloricacid. After the addition of 60 parts of glacial acetic acid, a solution rendered alkaline with sodium hydroxide of 201 parts of 3.3'-dihydroxy-diphenylamine and 60 parts of glacial acetic acid are added simultaneously drop by drop in the course of 2 hours. Under the buffer action of the sodium acetate which is formed, the coupling to form the trisazo-dyestuff takes place at a pH-value of 4. When the coupling is complete, the trisazo-dyestuff is combined in an alkaline medium with the diazo-suspension prepared from 173 parts of 1-aminobenzene-4-sulfonic acid to form the tetrakisazo-dyestufi which is isolated in the usually manner. The grey-black powder so obtained is readily soluble in water and dyes the various kinds of leatherdeep black tints having a good fastness to light and resistance toinorganic and organic acids as well as to alkalies and formaldehyde.

Example 11 alkaline l-aminobenzcneA-suiionic acid -v d l-amino-S-hydroxynaphthalene-3.6-disulionic acid 4.4-diamino-diphenyi is mixed, while well stirring, with the diazo-suspension prepared from 173 parts of l-aminobenzene-4-sulfonic acid. Into the mixture so obtained an alkaline solution of 201 parts of 3.3'-dihydroxy-diphenyiamine and 100 parts by volume of a N-solution of sodium hydroxide are introduced so that the coupling takes place in a strongly alkaline medium. -When the coupling is complete, the tetrakisazo-dyestuif is isolated in the usual manner, filtered off with suction and dried. It dyes the various kinds of leather deep covered black tints of good fastness properties.

In the following table are given a number of further polyazo-dyestufls of this invention which dye leather similar tints having the same good fastness properties:

Constitution Tint '1. 1 amino 4 acetaminobcnzene 2 sulfonic acid blue-black.

1 aminoi 8 hydroxynaphthaienc 3.6 disulionic acid 4.4 diamino diphcnyl 3.3 dihydroxy diphenylamine.

.2. 1 ammo 2 methyl 3 chiorobenzcne 5 sulionic acid 1 amino 8- hydroxynaphthalene 3.6

black.

ac sull'onic acid 4.4 diamino diphenyi 3.3-dihydroxy-dipl1enyiamine.

reddish black.

Tint 1 aminobenzene 4 suifonic acid 1 aminoacid 8 hydrcxynaphthalene 4.6 disulfonic acid 4.4 diamino diphenyl 3.3 dihydroxydiphenylamine.

1 amino 4 methylbenzenc 3 sulfonic acid 1- -amino1&8 hydroxynaphthaiene 3.6 disulfonic acid 4.4 diamino diphenyl 3.3- dihydroxy-diphenylamine.

1 aminobenzene 3 suiionic acid 1 am go- 8 hydroxynaphthalene 3.6 disulfonic acid t- 4.4 diammo diphenyl -r 3.3 dihydroxydiphcnylamine.

. 4 amino 1.1 azcbenzcnc 4 sulicnic acid 1 amino& 8 hydroxynaphthalenc 3.6 disuli'onic aci acid 4.4 diamino diphenyl 3.3- dihydroxy-diphenyiamine. 2 aminonaphthalene 5.7 disulionic acid --r 1- aminio 8 hydroxynaphthalenc 3.6 disulionic acid aci 4.4 diamino diphenyl -v 3.3 dihydrcxy diphenyl amine.

. 1 amino 3 chlorobcnzcne 4 sulfonic acid 1- amiio 8 hydroxynaphthalene 3.6 disuli'onic acid 4 4.4 diamino diphenyl 3.3 dihydroxy-diphenyiamine.

. 1 amino 4 hlorobcnzene 3 sulfonic acid 1 aminoni 8 hydroxynaphthaleno 3.6 disulionic acid 1- 4.4 -diamino -diphenyl 3.3- dihydroxy-diphcnylamine.

. chlorotoiuidinc sulfonic acids 1 amino 8- aci hydtoxynaphthalcnc 3.6 disulfonic acid 4.4 diamino diphenyi --v 3.3 dihydroxydiphenylamine.

1 aminonaphthalene 6 (7) sulfonic acid (mixture of Cievc's acids) -v 1 amino 2:1- hydroxyaci naphthalene 3.6 disulfonic acid 4-- 4.4 diamihrlio diphenyl 3.3 dihydroxy diphenylam e 1 amino 2 methyl 3 chlorobenzene 5 sulicnic acid 1 amino 8 hydroxyuaphthaiene 3.6 d sulacid fonic acid 4.4-diamiuo-diphenyl 3.3- dihydroxy diphenyiamine 1 amino 2 methyl 3 chiorobenzene 5 sulfonic acid.

. 1 aminonaphthalene 6 (7) suifonic acid (mixture of Cieve's acids) l-ami nloc-hydmxynaphthaaci lene 3.6 disulionic acid 4.4- diamino diphenyl 3.3-dihydroxy-d i p h e n y 1 a m in e 4- l-aminonaphthalene-fi (7)-suiionic acid (mixture of Cleve's acids).

. 1 amino 4 mcthylbenzcne 3 sulionic acid 1 aminoki 8 hydroxynaphthalene 3.6 disulfonic acid 4.4-diaminodiphenyl 3.3'-dihydroxy-diphenylaminc 1-amin0-4-methyibenzcne-3-sulfonic acid. l-aminobenzene-4sulfonic acid l-amiio-s hyaci droxynaphthalcne 4.6 disulfonic acid 4.4- diamino diphenyl 3.3- dihydroxy diphenylaminc i-aminobcnzeneA-sulionic acid. 1-aminobenzeue-2-suiionic acid i-anino-ii-hyc droxynaphthaiene-3.6-disulfonic acid 4.4-diamino diphenyl 3.3- dihydroxy diphenylamine 4- 1 aminobenzene 2 sulfonic acid.

l-aminobenzene-Ii-sulionic acid 1-amino-8-hyacid droxynaphthalene 3.6 disulfonic acid 4.4- diamino diphenyl 3.3- dihydroxy diphenylamine 1-aminobenzenc-3-suiionic acid.

. l-aminobenzeneA-sulfonic acid l-amino-iirhyacid droxynaphthalene 3.6 disuifonic acid 4.4- amino 3.3- dimethyl diphenyi 3.8- dihydroxy diphcnylamine 1 aminobcnzenc -4 sufoniacid.

. 1-amincbenzene-2.5-disulfonic acid 1- amino8- acid hydroxynaphthalene-3.6-disulfonicacid 4.4- diarninodiphenyl 3.3'- dihydroxy diphenylamine 1-aminobcnzene-2.5-disulionic acid.

. 1 amino 4 chlorobcnzcnc 2 sulfonic acid 1 aminoki 8 hydroxynaphthaiene 3.6 disulfonic ac acid 4.4 diamino-diphenyl 3.3- dihydrcxy-diphenyiamine 1 amino-4-chlorobenzenc-2'suifonic acid. 1 amincbenzenc -4 sulfonic acid 1 amino-8- aci hydroxynaphthalenc 4 sulfonic acid 4.4- diaminodiphenyl 3.3 -dihyd.roxy-diphenylamine 1 aminobenzcne 4 suiionic acid.

. 1 amino 3 nitrobenzcne 4 sulionic acid 1 aminchi 8 hydroxynaphthaiene 3.6 disuiicnic acid 4--- 4.4-diamono diphenyl -o 3.3-

dihydroxy-diphenyiamine 1 amino 3 nitrobcnzeneA-suiionic acid.

black.

greenish black.

black.

blueblack.

reddishblack.

black.

reddishblack.

bluishblack.

black.

blueblack.

greenishblack.

black.

greenishblack.

black.

bluishblack.

violet.

biuabiack.

from the group consisting of 1 and 2, and Y is a member selected from the group consisting of hydrogen and the sulfonic acid group.

We claim: 7 1. Polyazo-dyestufis corresponding to the following general formula wherein R and R represent members selected from the 2. Polyazo-dyestufis corresponding to the following gengroup consisting of benzene, sulfobenzene, disulfobenzene, eral formula OH OH on NH, I

R1-N=N -N=N N=N N=N-R,

wherein R and R represent radicals of the benzene series and Y stands for a member of the group consisting 0 hydrogen and the sulfonic acid group.

3. The polyazo-dyestutf corresponding to the following formula chloro-sulfobenzene, methyl-sulfobenzene, methyl-chlorosulfobenzene, nitrobenzene, nitro-sulfobenzene, acetamino-sulfobenzene, carboxybenzene, phenylarnino-nitrosulfobenzene, sulfo-phenylazobenzene, mono-sulfonaph- 2 thalene and di-sulfonaphthalene, R and R are radicals on on on lTIHz I Hogs -so,rr

selected from the group consisting of hydrogen, methyl, 4. The polyazo-dyestufi corresponding to the following nitro, chloro, methoxy, sulfo and carboxy radicals, X is 85 formula OH NH:

H033 SOaH a member selected from the group consisting of 5. The polyazo-dyestuff corresponding to the following formula OH NHI References Cited in the file of this patent UNITED STATES PATENTS Leeman et a1. Nov. 1, 1932 Huss et a1. Jan. 15, 1957 

1. POLYAZO-DYESTUFFS CORRESPONDING TO THE FOLLOWING GENERAL FORMULA 